Bituminous bonding compounds



BITUMINOUS BONDING COMPOUNDS Clarence F. Huber, Mount Healthy, and Paul F. Thompson, Deer Park, Ohio, assignors to The Cincinnati Milling Machine Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Application March 15, 1955 Serial No. 494,569

13 Claims. (Cl. 260-4045) prove the bonding eifectiveness of the bituminous composition but also exhibit improved thermal stability as compared with the bonding agents previously used.

It is known in the art of manufacturing bituminous compositions that the coating and bonding qualities of such compositions when mixed with mineral aggregates in the construction of asphalt pavements can be improved by addition thereto of certain chemical agents. The use of these agents has made it possible to use wet aggregates in preparing paving mixtures, thus making it unnecessary to have dry aggregates available and eliminating delays in road construction. Also the incorporation of such bonding agents in bituminous paving compositions has made it possible to use hydrophilic aggregates whichcould not be otherwise used. Moreover the use of these chemical bonding agents has brought about an improvement in the structural stability of the: finished bituminous pavement by decreasing the tendency of the aggregate and bitumen to separate when exposed to'water. Thus these agents have been useful in improving the method of asphalt road construction and improving'the quality and length of service of the finished pavement.

However, in general these previously proposed bonding agents have been subject to the deficiency thatthey do not remain stable at elevated temperatures. In many instances it is common practice to store bituminous compositions, after they have been prepared, in tanks at an elevated temperature of say 250 400 F. and maintain them in-a fluid state so that the composition can be readily removed without the re-hea'ting' that would be necessary if the composition-we're allowed to cool and solidify. The period of storage maybe as long as 14 days. In other cases quantities of asphaltor light bitumen are heated as high as 400-500 F. at the time of shipment so that the temperature upon arrival at the point of destination will have dropped to about 300- 350 R, which is the desirable temperature required for proper application 'in preparing the paving mixture.

In general the previously proposed bonding agents are incapable of withstanding such elevated temperatures; when subjected to such temperatures they rapidly lose their effectiveness and become of little value as bonding agents. Accordingly it is an object of the present invention to provide a novel group of compounds which are adapted to-be incorporated in bituminous paving compositions to improve the coating properties of the composition for wet aggregates and which retaintheir bonding effectiveness when subjected to the elevated temperatures encountered during the storage and handling.

of asphalt compositions. In accordance with the present invention the foregolng objective is achievedby incorporating in bituminous com- 2,874,174 Ratented Feb. 17, 1959 ice positions one or more compounds selected from the class. of amides of N,N,N-tri(aminoalkyl) amines and their salts] It has been found that when small amounts 'of' such compounds are incorporated in a bituminous composition, the coating and bonding properties of the composition for wet aggregates is substantially improved and this improvement is retained even when the b1- jtumiuous composition is maintained .at elevated temperatures for extended periods of time.

The amides and amide salts of the present invention include the nine classes indicated below.

(1) Mono-amides having the general formula: RCO-NH-A H2NA-N HzN-A wherein RC0 is an acyl group derived from an organic acid having from .10-20 carbon atoms, and A is an aliphatic hydrocarbon group having from 2-6 carbon atoms. In this formula the three A groups may hav different numbers of carbon atoms.

(2) Di-amides havingthe general formula:

ROO-NHA RGONHAN H2NA wherein RC0 is an acyl group derived from an organic acid having from 2-20 carbon atoms and A has the same definition as in Formula 1. In this formula the two RCO groups maybe diiferent and at least one RCO group should be derived from acid containing 10-20 carbon atoms. 1

(3) Tri-amides having the general formula:

RCO NH-A RCO.l IH- A-N RCO-NHA. wherein RC0 is an acyl group derived from an organic acid having from 2-20 carbon atoms; A is defined as in Formula 1; the three RCO groups may be different; and at least one RCO group is derivedfrom an acid having 10-20 carbon atoms. I

(4) A mono-amide-mono-salt having the general formula:

Roo-Nn-l "H. N-A N Hooo1t v H2N-A wherein RC0 is an acyl group derived from an acid having 10-20 carbon atoms; A is defined as in Formula 1; and the two RCO groups may be dilferent.

(5) A di-amide-mono-salt having the general formula:

HaN-A with the present invention are:

(7) A mono-amide-disalt having the general formula;

RCONHA HzNA-N .2(HOOCR) Hall-A v I t wherein RC is an acyl group derived from an acid having 2-20carbon atoms; A has the same definitions as in Formula 1; the RC0 group of the amide-forming acid and at least one of the other RCO groups is derived from an acid containing from -20 carbon atoms; and the several RCO groups may be diflerent.

Typical compounds that come within the scope of the foregoing general formulae and are useful in accordance named N,N bis(3 butyrylaminopropyl N (3-linoleoylaminopropyl) amine;

Q11H31C ONHCHICHZCHICHQCHlCH? NCHCH2NHG O CisHai HI crnomNno 0 011K named N- (6-linoleoylaminohexyl -N-( 3-oleoylaminopropyl)-N-(2-palmitoylaminoisopropyl)amine. This is one of the several compounds formed by acylation with three different fatty acids.

named N (3 aminopropyl) N,N bis( 3 palmitoylaminopropyl)amine;

C H CONHCH CH CH N CH CH CH NH 2 named N,N-bis(3 aminopropyl) N (3 oleoylaminopropyl) amine;

onHno oNncmon OHHMC ONHCHQOHFN.CX1H35CO 0H 01711340 ONHCHzCHzCHa named stearic acid salt of N-(2-linoleoylaminoethyl)-N- (3 oleoylaminopropyl) N (2 palmitoylaminoisop1'opyl)amine. This is one of several compounds formed by acylation with three dilferent fatty acids.

C H CONHCH CH CH N V (CH CH CH NH C H COOH named oleic acid salt of N,N-bis(3-aminopropyl)-N-(3- palmitoylaminopropyl) amine; C17HasCONHCH CH-2CH2 N (CH2CH2CH2NH2 2. C17Ha1COOH. CisHznCO OH Crr'HaoCO OH named mixed linoleic, palmitic, and stearic acid salt of N,N-bis( 3-aminopropyl -N- 3-oleoylaminopropyl) amine;

named palmitic acid salt of N,N-bis(Ii-oleoylaminopropyl) -N-( B-aminopropyl amine.

In preparing the amides and amide salts of the present invention, organic acids are reacted with tris(aminoalkyl) amines; 'Representative amines of this class that may be used are: (H N-CH CH N, named N,N,N-tris(2- aminoethyl)amine; (H NCH CH(CH )gN, named N,N,N-tris Z-aminoisopropyl amine;

named N ,N,N-tris(6-aminohexyl)amine;

named N-(Z-aminopropyl) -N-(2-aminoethyl)-N-(6-aminohexyl) amine.

As pointed out above, the acyl group of the salt-forming acid and at least one of the amide forming acyl groups should be derived from an organic acid having 10-20 carbon atoms and representative acids of this group, that may be used are: oleic, linoleic, linolenic, lauric, palmitic, stearic, rosin acid, abietic acids, naphthenic "acids, tall oil acids, or any acids derived from tall oils as well as mixtures of the foregoing acids. In cases where the present compounds contain more than one amide-forming acyl group, including at least one acyl group derived from an acid having 10-20 carbon atoms,

the other acyl groups of the compound may be derived from acids containing fewer than '10 carbon atoms. Representative acids of this group are: acetic, butyric, 2-ethylhexanoic, hexoic, caprylic, caproic, toluic, benzoic and Z-ethyI-butyric acids.

'In preparing the amido-amines of the present invention a tri (aminoalkyl) amine is mixed with a suitable organic acid, acyl halide, or ester and heated at 200 C. with agitation. The reaction with an organic acid may be considered as taking place in two stages; upon mixing, the amine salt of the organic acid is formed and during the heating process the salt is de-hydrated with the elimination of 1 mol of water for each amide group. The methods of making compounds of the type represented by Formulae 1-9 are indicated below.

To make'the compounds of Formula 1 equimolar quantities of acid and amine are mixed to form an amine salt which is heated to convert the amine salt to an amide according to the following equations:

The compounds of Formulae 2 and 3 may be prepared .111 the same way .as those of Formula 1 except that two and three mols of acid respectively are: used per'mol of amine.

NHr-A NHr-A-N+2RGOOH NH:A

R 0 OHLNHz-A RC ONHA RC Q-OH.NHzA-N no O-NH--AN 2320 In preparing the compounds of Formula 4 equimolar quantities of acid and amine are mixed and heated to form an amide, and then a second mol of acid is mixed with the amide to form the salt.

NHz-AN .(HOOCR) rim-A The compounds of Formula 5 can be made by making a' diamide as in Formula 2 and then mixinga mol of acid therewith to form the salt.

The compounds of Formula'6 can be made by making a triamide as in Formula 3 and then mixing a mol of acid therewith to form the salt, or they can also be made by the direct reaction of four mols of acid with one mol of the amine. a

.The compounds of Formula 9 can be made. by preparing a diamide as in Formula 2 and then mixing two mols of acid therewith to form a salt.

It will be evident that in the case of compounds such as those of Formulae 2 and 3, the compounds can be prepared by the addition of one mol of acid at a time with subsequent heating to form an amide group. Also where the several acyl groups of the compounds are derived from different acids, stepwise amidation is preferable to use, but simultaneous amidation can be carried out by using a mixture of the required acids.

' In order to point out more fully the nature of the present invention the following specific examples are given of illustrative methods of making certain of the present compounds:

Example I A mixture of three mols of linoleic acid and one mol of N (2 aminoethyl)-N-(Z-aminoisopropyl)-N-(6-aminohexyl) amine was heated for six hours with agitation at C. Approximately three mols of water was distilled ofi during this time. The material was cooled and mixed with one mol of oleic acid, giving the oleic acid salt of N (2 linoleoylaminoethyl) N (2-linoleoylaminoisopropyl) -N-(6-linoleoylaminohexyl) amine. The product was thermally stable in asphalt and was an effective agent for bonding asphalt to wet aggregate.

Example 11 Example 111 One mol of material prepared as in Example II was mixed with two mols of tall oil. The resulting material, which was a di-tall oil acid salt of N,N-bis(2-aminoethyl)- N-(2-palmitoylaminoethyl) amine, was thermally stable in asphalt and was an effective agent for bonding asphalt to wet aggregate.

Example IV A mixture of one mol of N-(2-aminoethyl)-N- (2- aminoisopropyl)-N-(6-aminohexyl) amine, one mol of oleic acid, one mol of linoleic acid, and one mol of palmitic acid was stirred and heated for six hours at 150 C. The product which was a mixture of triamides of these three acids, was thermally stable in asphalt and was an effective agent for bonding asphalt to wet aggregate.

It has been found that when suitable quantities of the foregoing compounds, usually 0.1 to 5% by weight, are incorporated in asphalt they confer on the asphalt the ability to eifectively coat wet aggregates and the improved coating and bonding properties of the asphalt are retained even when it is maintained at elevated temperatures for extended periods of time. Intact it has been found that the effectiveness of the present compounds is sometimes enhanced by heating in asphalt, possibly due to the fact that compounds such as those represented by Formulae l to 5 and 7 are capable of reacting with further quantities of acid and may reactvwith the naphthenic acids present in the' asphalt.

It is of course to be understood that the foregoing examples are illustrative only and that numerous amidoamines and salts other than.those.specifically referred to fall within the scope of the general formulae given above and can be incorporated in asphalt to achieve the advantages outlined at the beginning of the present specification.

We claim:

1. Compounds adapted to be incorporated in bituminous compositions to improve the coating properties thereof, said compounds being amides of' tris (aminoalkyl) aminesand salts of such amides, the amide-forming acids being organic acids having from 2 to 20 carbon atoms, and the salt-forming acids, if present, and at least one of. the amide-forming acids having from. 10 to 20 carbon atoms.

2. Compounds adapted to be incorporated in bituminous compositions to improve the coating properties thereof and having the. general formula:

wherein RC is an acyl group derived from an organic acid having 2-20 carbon atoms, at least one of said RCO groups is derived from an acid having -20 carbon atoms, and the several RCO groups can be different; and A is an aliphatic hydrocarbon radical containing 2-6 carbon atoms, and the several A radicals can be different.

3. Compounds adapted to be incorporated in bituminous compositions to improve the coating properties thereof and having the general formula:

wherein RC0 is an acyl group derived from an organic acid having 22() carbon atoms, at least one of said RCO groups contains 10-20 carbon atoms, and the two RCO groups can be different; and A is an aliphatic hydrocarbon radical containing 2-6 carbon atoms, and the several A radicals can be different.

4. Compounds adapted to be incorporated in bituminous compositions to improve the coating properties thereof and having the general formula:

wherein RC0 is an acylgroup derived from an organic acid having 10-20 carbon atoms; and A is an aliphatic hydrocarbon radical containing 2-6 carbon atoms, and the several A radicals can be different.

5. Compounds adapted to be incorporated in bituminous compositions to improve the coating properties thereof and having the general formula:

wherein RC0 is an acyl group derived from an organic acid having 220 carbon atoms, the RC0 group of the salt-forming acid and at least one other RCO group having 10-20 carbon atoms, and the several RCO groups may be different; and A is an aliphatic hydrocarbon radical containing 2-6 carbonatoms, and the several A radicals can be different.

6. Compounds adapted to'be incorporated in bituminous 8' V compositions to improve the coating properties thereof and having the general formula:

wherein RC0 is an acyl group derived from an organic acid having 22() carbon atoms, the RC0 group of the salt-forming acid and at least one other RCO group having from 10-20 carbon atoms, and the several RCO groups can be different; and A is an aliphatic hydrocarbon radical containing 2-6 carbonatoms, and the several A radicals can be different.

7. Compounds adapted to be incorporatedin bituminous compositions to improve the coating properties thereof and having the general formula:

wherein RC0 is an acyl group derived from an organic acid having 2-20 carbon atoms, the RC0 group of at least one of the salt-forming acids and at least one of the amide-forming RCO groups having from 10-20 carbon atoms, and the several RCO groups can be different; and A is an aliphatic hydrocarbon radical containing 2-6 carbon atoms, and the several A radicals can be different.

8. Compounds adapted to be-incorporated in bituminous compositions to improve the coating properties thereof and having the general formula:

wherein RC0 is an acyl group derived from an organic acid having 10-20 carbon atoms, and the two RCO groups can be different; and A is an aliphatic hydrocarbon radical containing 2-6 carbon atoms, and the several A radicals can be different.

9. Compounds adapted to be incorporated in bituminous compositions to improve the coating properties thereof and having the general formula:

wherein RC0 is an acyl group derived from an organic acid having 2-20 carbon atoms, the RC0 group 'of at least one of the salt-forming acids and amide-forming RCO group having from 10-20 carbon atoms, and the several RCO groups can be different; and A is an aliphatic hydrocarbon radical containing 2-6 carbon atoms, and the several A radicals can be different.

10. Compounds adapted to be incorporated in bituminous compositions to improve the coating properties thereof and having the general formula:

.(HO-OCR) rro-oon wherein RC0 is an acyl group derived from an organic acid having 2-20 carbon atoms, the amide-forming RCO group and at least one other RCO group having from 10-20 carbon atoms, and the several RCO groups can be different; and A is an aliphatic hydrocarbon radical containing 2-6 carbon atoms, and the several A radicals can be different.

11. A compound adapted to be incorporated in a bituminous composition to improve the coating properties thereof, said compound being N-(2-linoleoylaminoethyl)- N (2 linoleoylaminoisopropyl) N (6-linoleoylaminohexyl) amine.

12. A compound adapted to be incorporated in a bituminous composition to improve the coating properties thereof, said compound being N,N-bis(2-aminoethyl)-N- (Z-palmitoyl-aminoethyl) amine.

13. A compound adapted to be incorporated in a bituminous composition to improve the coating properties thereof, said compound being a di-tall oil acid salt of N,N bis(2 aminoethyl) N-(2-pa1mitoy1aminoethyl)- amlne.

References Cited in the file of this patent UNITED STATES PATENTS Kaplan Sept. 17, 1946 Johnson Apr. 22, 1947 UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,874,174 February 17, 1959 Clarence F. Huber et a1. It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, lines 74 and 75, for that portion of the formula reading (117E340 0NHCHgCHaCHg read (111E830 onnomomcm column 4:, line 11, right-hand portion of the formula for .CnHuC O OH read .CnHnG 0 on column 5, lines 27 to 30, fight-hand portion of the formula should appear as shown below instead of as in the patent:

Signed and sealed this 28th day of July 1959.

Attest: KARL H. AXLINE, ROBERT C. WATSON, Attesting Ofiaer. 'C'ommz'ssz'omr of Patents. 

1.COMPOUNDS ADAPTED TO BE INCORPORATED IN BITUMINOUS COMPOSITIONS TO IMPROVE THE COATING PROPERTIES THEREOF, SAID COMPOUNDS BEING AMIDES OF TRIS (AMINOALKYL) AMINES AND SALTS OF SUCH AMIDES, THE AMIDE-FORMING ACIDS BEING ORGANIC ACIDS HAVING FROM 2 TO 20 CARBON ATOMS AND THE SALT-FORMING ACIDS, IF PRESENT, AND AT LEAST ONE OF THE AMIDE-FORMING ACIDS HAVING FROM 10 TO 20 CARBON ATOMS. 